Secondary ethers of polyhydric alcohols



Patented May roe strays,

' .snconmny crimes or ALCO PATENT orric PoLrnYpmo HOLS Theodore W. Evans, Berkeley, itnd Edwin F.

Bullard, Oakland, Calif., assignors to Shell Development Company, San Francisco, Calif a corporation of Delaware No Drawing. Original application December 12,

1936, Serial No, 115,636. Divided and this applicationFebruary'll, 1938, Serial No. 190,029

8 Claims. (Cl. zoo-615' 10 and are also valuable as intermediates in the preparation of useful trihydric alcohols and other derivativesthereoi. A iurther object of the invention lies in the preparation of new intermediates from which the herein disclosed ethers may be readily prepared.

Secondary ethers of polyhydric alcohols 01 the class consisting of aliphatic trihydric alcohols, one hydroxy group of which has been substituted by the alkoxy group of an aliphatic secondary alcohol; aliphatic trihydric alcohols, two hydroxy groups of which have been substituted by the ,alkoxy groups of aliphatic secondary alcohols, at least one of, said alkoxy groups containing at least, i'our carbon atoms; and aliphatic trihydric alcohols, each hydroxy group of which has been substituted by the alkoxy group of an aliphatic secondary alcohol, have been prepared and described for the first time.

" The invention is described with particular reference to the secondary others of the glycerols, the term glycerol embracing, in addition to glycerolyits homologues, analogues and trlhydric substitution products. Secondary monoethers of the secondary hexylethers of glycerol, thesecwondary heptyl others at glycerol and thelike and their homologues; analogues I and suitable substitution'products; alpha isopropyl ether of beta- 45 methyl glycerol, beta isopropyl ether of betavmethyl glycerol, alpha secondary butyl ether oi betarmethyl glycerol, "beta-secondary hutyl ether 'o'fbeta-methyl glycerol,- alpha secondary amyl ether oifl beta-methylglycerol, the secondary 5o hexyl ethers ofibeta-methyl glycerol, the secondaryheptyl others oi' beta-methyl glycerol and the like and their homologues, analogues and suitable substitution products; the isopropyl. secondary butyl, secondary amyl, secondary hexyl, secondary heptyl and the like monoethers oi the beta-ethyl-, beta-propyl-, beta-hexyland the like glycerols; the isopropyl, secondary butyl, secondary amyl, secondary hexyl, secondary heptyl andthe like monoethers of the alphamethyl, alpha-ethyl-, alpha propyl and the like glycerols; as well as the secondary monoethers of the alpha alpha substituted glycerols as alpha methyl, alpha"-ethyl glycerol, alpha beta sub-- stituted glycerols as alpha inethyL-beta-methyl glycerol and the like.

It is seen that, in the above described novel compound, one hydroxy group of the trihydric alcohol has been replaced by the alkoxy group,

of an aliphatic secondary alcohol as'isopropyl alcohol, secondary butyl alcohol; secondary amyi alcohol, etc. One or both of the other hydroxy groups may be substituted by the alkoxy, aralkoxy or aryloxygroups ,of primary or tertiary alcohols or of phenolic compounds, why the negatlve radicals of aliphatic carboxylic acids, such as in alpha-methyl, alpha secondary butyl diether of glycerol, allyl, secondary'butyl diether of glycerol and phenyl, secondary butyl'diether of glycerol.

Disecondary diethers of glycerols, which are within the scope of the invention, include, among othersQthe following: alpha isopropyl, alpha secondary butyl diether of glycerol, alpha, beta diisopropyl diether of glycerol, alpha, alpha disecondary butyl diether of glycerol, alpha lsopropyl, alpha. secondary amyl diether of glycerol, alpha secondary butyl, alpha secondary amyl diether of glycerol, alpha, alpha disecondary amyl diether of glycerol, alphaisopropyl, alpha secondary hexyl diether of glycerol, alpha secondary butyl, alpha. secondary hexyl diether of glycerol, alpha secondary butyl, beta secondary butyl dietheroi glycerol, alphasecondary butyl, beta isop'ropyl diether of glycerol, alpha, alpha diisopropyl dietherofbeta-methyl glycerol, alpha, alpha or disecondary butyl diether of betamethyl glycerol, alphabets, diisopropyl diether of beta-methyl glycerol, the symmetrical "and mixed disecondary diethers of the beta-ethyh; betaprOpyLbeta-butyland thelike glycerol s, the symmetrical and mixeddiseconda'ry 'dlethers of the alpha substituted glycerols, and the like and their homologues, analogues and suitable substitution products. The remaining hydroxy groupjofthe above-listedfdisecondary diethers of glycerols may be substituted by the alkoxy, aralkoxy or aryloxy group of a primary or tertiary alcohol or of a, phenolic compound, or it may be substituted by the negative radical of an organic carboxylic acid.

Trisecondary triethers of glycerols, which are within the scope of the invention, include, among others, the following: triisopropyl triether of glycerol, trisecondary butyl triether of glycerol,

trisecondary amyl triether of glycerol, trisecondary hexyl triether of glycerol, alpha, alpha diisopropyl, beta secondary butyl triether of glycerol, alpha, beta diisopropyl. alpha secondary butyl triether of glycerol, alpha, alpha diisopropyl betasecondary amyl triether of glycerol,

alpha, alpha disecondary butyl, beta isopropyl triether of glycerol, and the like trisecondary triethers of the glycerols as beta-methyl glycerol, beta-ethyl glycerol, beta-propyl glycerol, alphamethyl glycerol, alpha. alpha dimethyi glycerol,

etc., wherein the hydron groups are substituted by the same or different alkyl radicals of aliphatic secondary'alcohols.

A particularly useful and readily prepared group of the secondary ethers of polyhydric alcohols comprises the secondary monoethers, the disecondary diethers wherein one of the secondary alcohol radicals contains at least four carbon atoms, and the trlseccndary triethers of glycerol.

The secondary monoethers of glycerol may berepresented by the formulae:

R-O-CIh-CHOE-CEOH and HMORr-CHQOE wherein it represents the alkyl radical of an aliphatic secondary alcohol.

' The disecondary diethers of glycerol with as which we are principally concerned. may be repaesented by the formulae:

wherein R, R, and B" may be the same or different and represent alkyl radicals of aliphatic secondary alcohols.

In our United States Patent No. 2,067,385, which issued January 12, 1937, with which'the parent application of which this application is a division was copending and a continuation-inpart thereof, we have described and claimed a 0 process for the preparation of secondary polyhydric alcohol ethers, which procem comprises reacting a secondary-base oleiine, as propylene. secondary butylene, secondary amylene', etc., with an aliphatic polyhydric alcohol in the presence of a condensing agent, preferably-an acid-acting condensing agent, which promotes a condensing action between the oleflne and the alcohol. This process is. suitable for the production of some of the secondary ethers of trihydrlc alcohols 0 herein described. We have. in addition, discovered that there are other methods of pre paring such secondary ethers of trihydrlc al- .It is a good nitrocellulose solvent.

fled withanal kalimetal saltofthedesiredalt phatic secondary alcohol. For example, if it is desired to prepare the alpha'isopropyl ether of glycerol, dichlorhydrin may be reacted with the isopropyl alcoholate of sodium to yield the isopropyl' ether of glycidol which can be readily hydrated to the desired alpha isopropyl monoether of glycerol. This manner of preparing the secondary ethers of trihydric alcohols is described in detail in the illustrative examples.

The invention is illustrated but not limited by the following examples which describe the preparation of representative secondary 'ethers of trihydric alcohols. The parts are by weight.

' Emmille I l About 54.5 parts of sodium were dissolved in mixture heated atjabout C. for about 1.5

At the end "of this time, the mixture hours. was cooled, filtered to separate sodium chloride, and distilled under'a subatmospheric pressure. Two reaction products were isolated.

The lower boiling product (13. P. 52' O. at

14 mm. of mercury) was the secondary butyl ether of glycidol of the formula 0 olnr-on-o-onroom This novel compound has a specific gravity A part of the secondary butyl ether of glycidol was heated with water in the presence of a mineral acid and hydrated to the novel alpha secondary butyl glycerol ether of the formula Ci rCHO-CHs-OHOHCH|OH A good yield of this ether was obtained.

The higher boiling fraction separated by vacuum distillation of the initial reacted mixture was the novel alpha, alpha disecondary butyl diether of glycerol of the formula I omen-o-cm cuon-cnro-cu-clm H: Hz

(dof 0.9125

This ether is a solvent for nitrocellulose. It is only slightly soluble in water.

Example If About 51 parts of sodium were dissolved in about 750 parts of secondary amyl alcohol. This solution was stirred and maintained at room temperature while about parts of dichlorhydrin were added slowly over a period of about one hour. After all of the dichlorhydrin had been added, the temperature of the mixture was raised to about 90 C. and the stirring continued for about one hour. At the end of this time, the cooled mixture was distilled under a subatmospheric pressure to separate the reaction product from the precipitated salt. The first distillate s eaves This novel compound has a boiling temperature of 74 C. under a pressure of 16 mm. of mercury. Its specific gravity The glycidol ether possesses a limited water solubility and it is a good solvent for nitrocellulose.

The secondary arnyl ether of glycidol was hydrated to the corresponding alpha secondary amyl ether of glycerol by the following method: About 40 parts of the glycidol ether, 400 parts of water and 0.15 part of sulphuric acid were mixed and the mixture stirred and heated under reflux for about five hours. At the end of this time the reaction mixture was neutralized and distilled under a subatmospheric pressure. The alpha secondary amyl ether of glycerol was obtained in good yield. This compound boils at 102 C. under a pressure of 3 mm., audit has a specific gravity (01% of asset The novel secondary ethers of trihydric alcohols are for the most part colorless, more or less viscous liquids of high boiling temperature and negligible vapor pressure at room temperature. The secondary ethers, particularly the secondary monoethers, may be used as substitutes for glycerol in a great many processes. In numerous cases they are more advantageously used than the glyeerols because of their lower hygroscopicity and greater solvent power for certain materials. For example, the secondary ethers of trihydric alcohols comprehended by the invention are useiul as ingredients of textile treatment media, as reagents in the manufacture of explosives, as

perfume fixatives, as constituents of lubricatingcompositions, as constituents oi. anti-freeze mixtures for use in the cooling systems of internal combustion engines, as heat-transferring media in indirect heat conduction systems, as reactants in the preparation of resins, etc.

The novel trihydric alcohol ethers are particularly useful as solvents.

plasticizers for cellulose ethers and esters. They may be used as such or admixed with other substances, as extracting agents for organic substances as alkaloids, essential oils, essences and the like. They are excellent solvents for acetylene, and they may be used as scrubbing agents to recover acetylene from gaseous mixtures. The glycerol ethers, particularly those of lower molecular weight, are excellent solvents for acidic saws, particularly hydrocyanic acid. Further, the secondary ethers of trihydric alcohols are useful intermediates. in the preparation of trihydric alcohols and trlhydric alcohol derivatives.

Many of them are .good nitrocellulose solvents and are useful as This aplication is a division of our copending application, Serial No. 115,636, filed December 12, 1936, whch was copending with application, Serial No. 722,567, filed April 26, 1934, which issued as United States Patent 2,067,385 on January 12, 1937.

The foregoing description has been made rather detailed for clearness of understanding only, and no unnecessary limitations should be understood therefrom, but the appended claims should be construed as broadly as possible in view of the prior art.

We claim as our invention:

1. An aliphatic trisecondary triether of a trihydric alcohol.

2. An aliphatic triseconary triether of a glycerol.

3. An aliphatic trisecondary triether of glycerol.

l. An aliphatic triether of a glycerol wherein at least one of the alkoxy groups is the allroxy group of a secondary aliphatic alcohol.

5. The glycerol triether oi the formula wherein R Rl and R2 are the alkyl radicals of aliphatic alcohols at least one of which is an aliphatic secondary alcohol.

6. The glycerol ,triseccndary triether of the formula I V wherein R, R1 and R2 represent the alkyl radicals of aliphatic secondary alcohols.

'7. The triisopropyl triether of glycerol.

8. The trisecondary butyl triether oi. glycerol.

THEODORE W. EVANS. EDWIN F. BUILAHD. 

